CN115504526A - Oxide sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents
Oxide sodium-ion battery positive electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115504526A CN115504526A CN202211352251.7A CN202211352251A CN115504526A CN 115504526 A CN115504526 A CN 115504526A CN 202211352251 A CN202211352251 A CN 202211352251A CN 115504526 A CN115504526 A CN 115504526A
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- Prior art keywords
- sodium
- salt
- ion battery
- oxide
- soluble
- Prior art date
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 103
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 115
- 229910052751 metal Inorganic materials 0.000 claims abstract description 97
- 239000002184 metal Substances 0.000 claims abstract description 97
- 238000001556 precipitation Methods 0.000 claims abstract description 73
- 239000011259 mixed solution Substances 0.000 claims abstract description 64
- 238000005245 sintering Methods 0.000 claims abstract description 61
- 238000002156 mixing Methods 0.000 claims abstract description 58
- 150000003839 salts Chemical class 0.000 claims abstract description 58
- 239000011734 sodium Substances 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 239000010405 anode material Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 30
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- 239000002861 polymer material Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 235000002639 sodium chloride Nutrition 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 39
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 38
- 239000004793 Polystyrene Substances 0.000 claims description 28
- 229920002223 polystyrene Polymers 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 11
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- 150000002505 iron Chemical class 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
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- 150000001868 cobalt Chemical class 0.000 claims description 3
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- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
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- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
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- 229960002089 ferrous chloride Drugs 0.000 claims description 2
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- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 239000011247 coating layer Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000012298 atmosphere Substances 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
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- 241000080590 Niso Species 0.000 description 12
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 description 12
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an oxide sodium-ion battery anode material and a preparation method and application thereof, wherein the chemical formula of the oxide sodium-ion battery anode material is NaxMO 2 X is more than 0 and less than or equal to 1,M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn; the preparation method comprises the following steps: (1) Mixing soluble metal M salt, a high polymer material and water to obtain a mixed solution; (2) Reacting the mixed solution with the precipitation solution to obtain a metal M precursor; (3) And mixing the metal M precursor with a sodium source, and sintering under an aerobic condition to obtain the oxide sodium-ion battery anode material. The invention leads the obtained oxidation to be realized through the design and the cooperation of the high polymer material and the coprecipitation methodThe positive electrode material has a specific structure gradually transited from inside to outside, has excellent structural integrity and stability and good electrochemical performance, and can be used as a positive active material to improve the multiplying power and the cycle performance of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to an oxide sodium ion battery positive electrode material and a preparation method and application thereof.
Background
With the development and progress of energy technology, lithium batteries have been widely used in the fields of energy storage, electric vehicles, consumer electronics, and the like, and become an indispensable component in the work and life of people at present. With the increase of the usage amount of lithium batteries, the problem of limitation of the reserves of common lithium battery resources such as lithium, nickel and the like is increasingly prominent, so that the price of raw materials of the lithium batteries is continuously increased in recent years, the cost performance of the lithium batteries is seriously reduced, and the application of the lithium batteries is influenced. In addition, the safety of lithium batteries is becoming a problem due to the continuous pursuit of energy density of lithium batteries. Sodium batteries, which are almost simultaneously available with lithium batteries, have recently come back into the sight of researchers, and compared with lithium batteries, sodium has higher reserves and wider sources, with the continuous maturity of technologies for extracting sodium from seawater, the price of sodium will continue to be lowered, which is an inherent advantage of the price of sodium batteries. In addition, because lithium batteries are easy to generate dendrites and the like, the potential safety hazard of short circuit spontaneous combustion is brought, and sodium batteries are difficult to form dendrites and have higher safety than lithium batteries. Therefore, under comprehensive consideration, although the energy density and the power density of the sodium battery are lower than those of the lithium battery, the sodium battery has great potential to fill the market gap between the lithium battery and the lead-acid battery due to the unique advantages of the sodium battery.
At present, the commercialized negative electrode material of the sodium battery is mainly hard carbon, and the positive electrode material comprises prussian, polyanion, oxide and the like; among them, the oxide-based positive electrode material has the characteristics of simple structure, easy preparation and high theoretical capacity, and is continuously concerned by researchers. The transition metal layered oxide is an important branch of the oxide-based positive electrode material, and the nickel-manganese-based layered oxide is more representative. Similar to the high nickel oxide anode material in the lithium battery, the gram capacity of the oxide has a direct relation with the Ni content, and the Ni content can be effectively increased by increasing the Ni contentHigh specific capacity of oxide-based positive electrode material. Research shows that too high Ni content can directly influence the structural stability of the oxide in the circulating process; due to Ni 4+ The material has higher activity in the electrolyte, and when the Ni content is higher than 60%, the cycling stability of the material is obviously reduced. In addition, when the voltage is higher than 4.0V, a series of side reactions occur between the oxide and the electrolyte, which further accelerates the degradation of the material properties.
In order to improve the stability of the oxide cathode material, surface coating is a common strategy in the industry, that is, a coating layer is constructed on the surface of the oxide material so as to separate the electrolyte from the oxide, avoid direct contact between the electrolyte and the oxide, and reduce side reactions, thereby playing roles in inhibiting phase change and improving the structural stability of the material. For example, CN109638273A discloses a coating method of a sodium ion battery positive electrode material, which uniformly mixes a layered oxide positive electrode material, a coating precursor and a solvent, then performs spray drying to obtain a positive electrode material coated by the coating precursor, and then performs secondary sintering on the above materials to form an oxide shell, thereby obtaining an oxide-coated layered oxide positive electrode material; wherein the content of the first and second substances, the coating precursor is one or a combination of more of oxides, nitrates and hydrates thereof, sulfates and hydrates thereof and organic salts of Al, mg, ti, zn, zr, nb or La. CN113889613A discloses a layered sodium ion battery anode material with a gradient structure, which is characterized in that a layered oxide anode material with a P2 phase structure is uniformly mixed with a magnesium source, and Mg is enabled to react by a low-temperature molten salt reaction method 2+ Diffusing into the layered oxide to form a layered oxide with a MgO coating layer and a gradient Mg 2+ A doped layered oxide positive electrode material. CN114613981A discloses a zinc-doped and zinc-oxide-combined manganese-based layered oxide material, and the preparation method comprises the following steps: the method comprises the steps of ball-milling and mixing a sodium source, a nickel source, a copper source, a zinc source and a manganese source according to a certain stoichiometric ratio, and then calcining at high temperature, so that zinc ions in the obtained product exist in a bulk phase structure of the P2 type layered oxide and are uniformly enriched on the particle surface of the P2 type layered oxide in a zinc oxide form, and the electrochemical performance of the P2 type nickel-manganese based layered oxide anode material is improved.
At present, the use of the compositionIn the oxide positive electrode material, a common coating layer material includes Al 2 O 3 、MgO、TiO 2 And oxides such as ZnO, and AlF are used in a small number 3 Or NaPO 3 Etc.; common coating methods include chemical methods, ball milling methods, atomic layer deposition techniques, and the like. However, the sensitivity of the sodium-electricity anode material to moisture brings many limitations to the implementation of the coating mode, and multiple times of sintering are usually required to complete the coating, thereby increasing the preparation difficulty and the production cost of the sodium-electricity anode material. Moreover, since the coating layer and the oxide cathode material have different compositions and structures, the introduction of the coating layer inevitably introduces the problem of the interface between the coating layer and the cathode material, affecting the ionic conductivity thereof. In addition, due to different material structures, it is difficult to ensure that the coating layer and the oxide cathode material maintain the same expansion coefficient in the charging and discharging processes, so that the coating layer is damaged or falls off, and the performance of the sodium battery is deteriorated. Therefore, the development of a positive electrode material for a sodium battery, which has more excellent performance, particularly better stability, is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an oxide sodium ion battery anode material and a preparation method and application thereof, wherein the surface of the obtained oxide sodium ion battery anode material has a special oxygen-deficient structure through the design and mutual cooperation of a high polymer material and a coprecipitation method, so that the in-situ modification and coating of an oxide are realized. The oxide sodium ion battery positive electrode material has excellent structural integrity, stability and electrochemical performance, and can improve the rate capability and cycle performance of a sodium ion battery when being used as a positive electrode active material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of an oxide sodium-ion battery anode material, wherein the chemical formula of the oxide sodium-ion battery anode material is NaxMO 2 Wherein x is more than 0 and less than or equal to 1,M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn; the preparation method comprises the following steps:
(1) Mixing soluble metal M salt, a high polymer material and water to obtain a mixed solution;
(2) Reacting the mixed solution obtained in the step (1) with a precipitation solution to obtain a metal M precursor;
(3) And (3) mixing the metal M precursor obtained in the step (2) with a sodium source, and then sintering under an aerobic condition to obtain the oxide sodium-ion battery anode material.
In the preparation method provided by the invention, a high molecular material and a soluble metal M are mixed by dissolving salt, and the high molecular material is introduced in the process of synthesizing a metal M precursor by a coprecipitation method, so that a composite structure of a hydroxide precursor and the high molecular material is formed in the obtained metal M precursor; the metal M precursor and the sodium source are mixed and then sintered, a high polymer material undergoes a series of carbonization and oxidation reactions, oxygen is taken away from the surface of precursor particles in a short time, and the oxygen in the structure is rapidly lost, so that the rapid loss of the oxygen on the surface of an oxide (layered oxide) prepared from the sodium source and the metal M precursor can cause the phase change of the oxide (layered oxide) from the layered structure to a rock salt phase, the gradual transition from the layered oxide to the rock salt phase from inside to outside is realized, the surface of the material in the obtained oxide sodium ion battery anode material has a stable oxygen-deficient structure, namely an oxygen-deficient modified coating layer is formed, the layer is synchronously formed in the process of forming the layered oxide from the sodium source and the metal M precursor, and has the characteristics of in-situ modification/coating, the modified coating layer and the bulk material (bulk phase) of the oxide have the same components, the structure is gradually transited from inside to outside, the modified coating layer is tightly combined with the bulk (bulk) of the oxide, and the generation of the interface between the coating layer and the bulk material is reduced. Meanwhile, the rock salt phase generated in situ is an oxygen-deficient structure, so that further loss of oxygen in the oxide can be prevented, and the thickness of the phase change layer can be controlled to be about 10 nm; in addition, in the preparation process, the rock salt phase generated by sintering can reduce the continuous generation of oxygen defects in the oxide and improve the structural integrity of a target product.
According to the invention, through the design and mutual cooperative cooperation of the high polymer material and the co-precipitation method, the oxygen distribution condition on the surface of the oxide is regulated and controlled to form an oxygen-poor stable phase, so that a coating layer which is the same as the components of the bulk material, tightly combined and stable in structure is generated in situ, the obtained oxide positive electrode material has a special structure gradually transited from inside to outside, the interface problem and the coating layer damage and shedding problem caused by conventional coating are avoided, the oxide sodium ion battery positive electrode material has excellent structural integrity, stability and electrochemical performance, and the effect of improving the cycle stability is achieved. The preparation method has the advantages of wide raw material source, no need of harsh reaction conditions and complex steps, simple process route and wide large-scale application prospect.
In the invention, the oxide sodium-ion battery cathode material is a layered oxide sodium-ion battery cathode material, and the "oxide" and the "layered oxide" described herein have the same meaning.
In the invention, M in the soluble metal M salt is NaxMO 2 M in (2) is any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn; the soluble metal M salt is selected from any one or the combination of at least two of soluble nickel salt, soluble manganese salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble titanium salt and soluble tin salt.
Wherein the "solubility" refers to solubility in water.
Preferably, the soluble metal M salt in the step (1) comprises a soluble nickel salt and a soluble manganese salt, and at least one of a soluble iron salt, a soluble cobalt salt, a soluble copper salt, a soluble titanium salt and a soluble tin salt; the obtained oxide sodium-ion battery positive electrode material is a nickel-manganese-based oxide sodium-ion battery positive electrode material.
Preferably, the soluble metal M salt of step (1) comprises a combination of a soluble nickel salt, a soluble manganese salt and a soluble iron salt.
Preferably, the soluble nickel salt comprises any one of nickel sulfate, nickel chloride, nickel nitrate or a combination of at least two thereof.
Preferably, the soluble manganese salt comprises any one of manganese sulfate, manganese chloride, manganese nitrate or a combination of at least two of the foregoing.
Preferably, the soluble iron salt comprises any one of ferrous sulfate, ferrous chloride, ferrous nitrate, or a combination of at least two thereof.
Preferably, the concentration of the soluble metal M salt in the mixed solution in the step (1) is 0.5-2.5mol/L, for example, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.2mol/L or 2.4mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Herein, "the concentration of the soluble metal M salt in the mixed solution" represents the sum of the concentrations of all the soluble metal M salts in the mixed solution.
Preferably, the polymer material in step (1) includes any one of polystyrene, polydopamine, polyacrylate, or a combination of at least two thereof.
Preferably, the polyacrylate is polymerized from acrylate monomers, and the acrylate monomers include any one or a combination of at least two of alkyl (meth) acrylate, glycidyl (meth) acrylate and hydroxyethyl (meth) acrylate.
Preferably, the polyacrylate comprises poly (glycidyl methacrylate).
Preferably, the mass of the polymer material is 0.2-6% based on 100% of the mass of the hydroxide (i.e. the theoretical mass of the hydroxide) prepared by the soluble metal M salt and the precipitation solution, for example, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or 5.5%, and the specific values therebetween are not limited to the space and for brevity, and the invention does not exhaustive list the specific values included in the range, and further preferably 1-5%.
According to the preferable technical scheme, the theoretical mass of the hydroxide obtained by calculation according to the using amounts of the soluble metal M salt and the precipitation solution is 0.2-6% in terms of 100% of the theoretical mass of the hydroxide, so that the polymer material generates a series of carbonization and oxidation reactions in the subsequent sintering process, the oxygen content and the oxygen distribution on the surface of the oxide material are regulated, and an oxygen-poor stable phase is formed on the surface, so that a coating layer which has the same component as an oxide body (bulk phase), has a different structure, is tightly combined and has a stable structure is generated in situ, and the oxide sodium-ion battery positive electrode material has excellent structural integrity, stability and electrochemical performance. If the quality of the high polymer material is too low, the oxygen content and the oxygen distribution cannot be effectively regulated, so that the structural stability and the cycle performance of the obtained anode material are poor; if the mass of the high polymer material is too large, on one hand, the thickness of the formed oxygen-poor layer is too high, and the electrochemical performance of the bulk material, including specific capacity, rate capability, stability and the like, is seriously influenced.
Preferably, the mixing method of step (1) comprises: dissolving soluble metal M salt in water to form an aqueous solution, adding a high polymer material into the aqueous solution, and uniformly dispersing to obtain the mixed solution.
Preferably, the method of dispersion comprises stirring dispersion and/or ultrasonic dispersion.
Preferably, the precipitation solution in step (2) comprises a combination of a precipitant and a complexing agent.
Preferably, the precipitating agent comprises sodium hydroxide and/or potassium hydroxide, further preferably sodium hydroxide.
Preferably, the complexing agent comprises any one of ammonia water, sodium citrate, disodium ethylenediaminetetraacetate (disodium EDTA), tetrasodium ethylenediaminetetraacetate (tetrasodium EDTA) or a combination of at least two of them, and further preferably ammonia water.
Preferably, the precipitation solution in the step (2) comprises a combination of sodium hydroxide and ammonia water.
Preferably, the concentration of the complexing agent (ammonia) in the precipitation solution is 0.12-2mol/L, for example, 0.15mol/L, 0.2mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, 1mol/L, 1.2mol/L, 1.5mol/L or 1.8mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the precipitant in the precipitating solution is 2.0 to 2.2mol based on 1mol of the soluble metal M salt in the mixed solution, for example, 2.02mol, 2.05mol, 2.08mol, 2.1mol, 2.12mol, 2.15mol or 2.18mol, and specific values therebetween, which is not intended to limit the disclosure and conciseness, the present invention is not exhaustive to list the specific values included in the range.
In the invention, the mixed solution comprises soluble metal M salt and a high molecular material, and when the mixed solution reacts (coprecipitation reaction) with the precipitation solution, the generated hydroxide precursor nucleates on the surface of the high molecular material to obtain the metal M precursor with a composite structure.
Preferably, the reaction of step (2) is carried out in a protective atmosphere.
Preferably, the protective atmosphere comprises a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.
Preferably, the reaction of step (2) is carried out in a continuous reactor, and the specific method comprises the following steps: and introducing the mixed solution and the precipitation solution into a continuous reactor simultaneously for reaction.
Preferably, the feeding rates of the mixed liquid and the precipitation liquid are 1-20mL/min, such as 2mL/min, 5mL/min, 8mL/min, 10mL/min, 12mL/min, 15mL/min or 18mL/min, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
Preferably, the reaction temperature in step (2) is 40-60 ℃, for example 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃ or 58 ℃, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction time in step (2) is 3 to 7 hours, for example, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours or 6.5 hours, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction of step (2) has a pH of 8 to 11.5, for example, 8.2, 8.5, 8.8, 9, 9.2, 9.5, 9.8, 10, 10.2, 10.5, 10.8, 11, 11.2 or 11.4, and specific values therebetween are not exhaustive for the invention and for the sake of brevity.
Preferably, the reaction of step (2) is carried out under stirring conditions.
Preferably, the stirring speed is between 800 and 1200rpm, which may be, for example, 850rpm, 900rpm, 950rpm, 1000rpm, 1050rpm, 1100rpm or 1150rpm, and the specific values therebetween are not exhaustive and are not intended to limit the invention to the specific values included in the ranges for brevity and conciseness.
Preferably, the reaction in step (2) further comprises the steps of washing and drying after the reaction is completed.
Preferably, the detergent for washing is water.
Preferably, the drying temperature is 60-100 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the drying time is 1 to 6 hours, for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or 5.5 hours, and the specific values therebetween are limited by space and for the sake of brevity, the invention is not exhaustive and the specific values included in the range are further preferably 2 to 5 hours.
Preferably, the first and second electrodes are formed of a metal, the sodium source in the step (3) is selected from any one of sodium oxide, sodium hydroxide and sodium salt or the combination of at least two of the sodium oxide, the sodium hydroxide and the sodium salt.
Preferably, the sodium source in step (3) comprises any one of sodium hydroxide, sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate and sodium chloride or a combination of at least two of the above.
In the present invention, the sodium source and the soluble metal M salt are respectively used in the amount of the target product NaxMO 2 The stoichiometric ratio of Na to each M was determined.
Preferably, the sodium source may be added in excess relative to the soluble metal M salt.
Preferably, the actual amount of the sodium source is 101-115%, for example 102%, 103%, 104%, 105%, 107%, 109%, 110%, 112%, 113% or 114%, based on 100% of the theoretically required sodium source, and the specific values therebetween, for reasons of space and brevity, the invention is not exhaustive and the range includes the specific values, and more preferably 101-105%.
Preferably, the mixing method in step (3) is grinding mixing.
Preferably, the mixing of step (3) is carried out in a high-speed mixer.
Preferably, the sintering of step (3) is performed in an air atmosphere.
In the present invention, the sintering in step (3) is performed in any apparatus capable of sintering known in the art, and preferably, the apparatus for sintering comprises a muffle furnace, a tube furnace, a rotary furnace, a box furnace, a pusher kiln or a roller kiln.
Preferably, the sintering in step (3) comprises a first stage sintering and a second stage sintering which are sequentially carried out, wherein the temperature of the first stage sintering is lower than that of the second stage sintering.
Preferably, the temperature of the first stage sintering is 400-550 ℃, for example, 410 ℃, 430 ℃, 450 ℃, 470 ℃, 490 ℃, 500 ℃, 520 ℃ or 540 ℃, and the specific values therebetween are limited for space and simplicity, and the invention is not exhaustive.
Preferably, the first sintering period is 3-7h, for example, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h or 6.5h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature of the second stage sintering is 750-900 ℃, for example 780 ℃, 800 ℃, 810 ℃, 830 ℃, 850 ℃, 870 ℃ or 890 ℃, and specific values therebetween are not exhaustive for the invention, and for the sake of brevity and conciseness, the specific values included in the range are not intended to be exhaustive.
Preferably, the second sintering time is 10-25h, for example, 11h, 13h, 15h, 17h, 19h, 20h, 21h, 23h or 24h, and the specific values therebetween are not exhaustive, but for brevity and conciseness.
Preferably, the preparation method specifically comprises the following steps:
(1) Mixing soluble metal M salt, a high polymer material and water to obtain a mixed solution; the concentration of soluble metal M salt in the mixed solution is 0.5-2.5mol/L;
the high polymer material comprises any one or the combination of at least two of polystyrene, polydopamine and polyacrylate; the mass of the high polymer material is 0.2-6% by taking the mass of the hydroxide prepared from the soluble metal M salt and the precipitation solution as 100%;
(2) Reacting the mixed solution obtained in the step (1) with a precipitation solution, wherein the pH value of the reaction is 8-11.5, the temperature is 40-60 ℃, the time is 3-7h, and the generated product is washed and dried to obtain a metal M precursor;
wherein the precipitation solution comprises a combination of sodium hydroxide and ammonia water, and the concentration of the ammonia water in the precipitation solution is 0.12-2mol/L; based on 1mol of soluble metal M salt in the mixed solution, the amount of the sodium hydroxide is 2.0-2.2mol;
(3) And (3) uniformly mixing the metal M precursor obtained in the step (2) with a sodium source, sintering for 3-7h at 400-550 ℃ under an aerobic condition, and then heating to 750-900 ℃ for sintering for 10-25h to obtain the oxide sodium ion battery anode material.
In a second aspect, the invention provides an oxide sodium-ion battery cathode material, which is prepared by the preparation method according to the first aspect.
The chemical formula of the oxide sodium-ion battery positive electrode material is NaxMO 2 Wherein M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn.
Wherein 0 < x ≦ 1,x may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95, and specific values therebetween, not to be limited in space and for brevity, the present invention is not exhaustive of the specific values encompassed by the stated ranges.
Preferably, x is 0.5 to 1, preferably 0.5 < x.ltoreq.1, more preferably 0.6 < x.ltoreq.1.
Preferably, the chemical formula of the oxide sodium-ion battery positive electrode material is NaxNiyMnzM' (1-y-z) O 2 (ii) a Wherein, 0 < y < 1,0 < z < 1,M' is selected from any one or the combination of at least two of Co, fe, cu, ti and Sn; therefore, the oxide sodium-ion battery positive electrode material is a nickel-manganese-based oxide sodium-ion battery positive electrode material.
Wherein 0 < y < 1,y may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9, and the specific point values therebetween are not exhaustive and for brevity, the invention does not provide an exhaustive list of specific point values included in the range, and further preferably 0 < y ≦ 0.5.
0 < z < 1,z may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9, and the specific values therebetween, are not exhaustive and for brevity, the invention does not provide an exhaustive list of specific values encompassed within the stated range, and further preferably 0 < z ≦ 0.5.
0＜y+z≤1。
Preferably, the chemical formula of the oxide sodium-ion battery cathode material is NaxNiyMnzFe (1-y-z) O 2 。
The invention combines the coprecipitation method with the high polymer material, effectively regulates and controls the surface oxygen distribution of the oxide through the optimized design of the preparation method, modifies the lamellar structure with the surface thickness of about 10nm, and arranges the modified lamellar structure on the surface of the materialForming an oxygen-deficient stable phase, namely forming a homogeneous oxygen-deficient coating layer; the coating layer and the oxide body have different structures and the same components, so that the problem of poor ionic conductivity caused by interface problems can be effectively avoided; and the structure of the coating layer is stable, the phenomenon of breakage or falling off cannot occur in circulation, and long-time continuous protection can be provided for the oxide cathode material. The oxide sodium-ion battery positive electrode material has a specific structure gradually transited from inside to outside, has excellent structural integrity and cycle stability, and has excellent ionic conductivity, capacity and electrochemical performance; the oxide sodium-ion battery positive electrode material NaxMO 2 The preferred x in (1) is 0.65-1 (P2 phase with x of about 0.67-0.7, O3 phase with x of about 0.7-1), and the higher sodium content provides sufficient Na + The electrochemical reaction is carried out, and the electrochemical reaction can be used as a positive electrode active material, so that the sodium ion battery has excellent capacity performance, rate performance and cycle performance.
Preferably, the specific capacity of the oxide sodium-ion battery positive electrode material at 0.1C is more than 138mAh/g, and can reach 138.1-138.7mAh/g.
Preferably, the specific capacity of the oxide sodium-ion battery positive electrode material at 0.5C is more than or equal to 126.9mAh/g and can reach 126.9-128.6mAh/g.
Preferably, the specific capacity of the oxide sodium-ion battery positive electrode material at 1.0C is more than or equal to 116.5mAh/g and can reach 116.6-118.2mAh/g.
Preferably, the specific capacity of the oxide sodium-ion battery positive electrode material at 2.0C is more than 99mAh/g, and can reach 99.2-100.5mAh/g.
Preferably, the specific capacity of the oxide sodium-ion battery positive electrode material at 5.0C is more than or equal to 84mAh/g and can reach 84.2-89.8mAh/g.
In a third aspect, the invention provides a use of the oxide sodium-ion battery positive electrode material according to the second aspect in an electrochemical device.
Preferably, the electrochemical device comprises a sodium ion battery or a capacitor.
In a fourth aspect, the present invention provides a sodium ion battery comprising an oxide sodium ion battery positive electrode material as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation method provided by the invention, through the design and mutual cooperative coordination of the high polymer material and the co-precipitation method, the oxygen distribution and oxygen content conditions on the surface of the oxide are effectively regulated and controlled to form an oxygen-poor stable phase, a coating layer which is the same as the components of the bulk material, is tightly combined and has a stable structure is generated in situ, and the obtained oxide anode material has a specific structure which is gradually transited from inside to outside, has excellent structural integrity and stability, has good electrochemical performance, and has excellent performances in the aspects of capacity, ionic conductivity and cycle performance. Moreover, the preparation method has the advantages of wide raw material source, simple process route and wide large-scale application prospect.
(2) The oxide sodium ion battery positive electrode material has excellent stability, specific capacity and rate capability, can be used as a positive electrode active material for a sodium ion battery, can effectively improve the rate capability and cycle performance of the sodium ion battery, has a capacity retention rate of not less than 83.1% at a cycle of 100 cycles of 0.5C and a capacity retention rate of not less than 63.5% at a cycle of 300 cycles of 2.0C, and has obvious breakthrough in performance under high rate.
Drawings
Fig. 1 is an XRD pattern of the oxide sodium-ion battery positive electrode material provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
"optionally" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Reference throughout this specification to "one embodiment," "some embodiments," "exemplarily," "a specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The raw materials involved in the following embodiments of the present invention are all commercially available products; among them, polystyrene (PS), available from Michelin (L815936, polystyrene microspheres, 0.05-0.1 μm); polydopamine was purchased from West An Jiyue organisms under the designation Q-0094192; poly (glycidyl methacrylate), available from mikrolin (G810680, poly (glycidyl methacrylate) microspheres).
Example 1
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding polystyrene with the mass of 1% into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the solution at 50 ℃ after dripping, heating and reacting for 5 hours, washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing in a high-speed mixer according to the stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, heating to 850 ℃ and sintering for 15h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 2
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding polystyrene with the mass of 2% into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dropwise adding the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, stirring speed to be 1000rpm, keeping the pH value of the solution in the reactor to be 10, keeping the temperature of 50 ℃ for reaction for 5 hours after dropwise adding the solution, and repeatedly cleaning and drying the generated product by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing in a high-speed mixer according to the stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, heating to 850 ℃ and sintering for 15h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 3
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding 3% by mass of polystyrene into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) mixing the raw materials to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the solution at 50 ℃ for reaction for 5 hours after dripping, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, heating to 850 ℃ and sintering for 15h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 4
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding polystyrene with the mass of 4% into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dropwise adding the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, stirring speed to be 1000rpm, keeping the pH value of the solution in the reactor to be 10, keeping the temperature of 50 ℃ for reaction for 5 hours after dropwise adding the solution, and repeatedly cleaning and drying the generated product by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, heating to 850 ℃ and sintering for 15h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 5
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding polystyrene with the mass of 5% into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the solution at 50 ℃ for reaction for 5 hours after dripping, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, heating to 850 ℃ and sintering for 15h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 6
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding 3.5% polystyrene by mass into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia water (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2.2mol/L, and the concentration of ammonia water is 0.25mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 45 ℃, controlling the stirring speed to be 900rpm, controlling the pH value of the solution in the reactor to be 10.3, keeping the solution at 45 ℃ after dripping, reacting for 7 hours, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 450 ℃ for 7h in an air atmosphere, heating to 900 ℃ and sintering for 12h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 7
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding 3.5% polystyrene by mass into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2.1mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dropwise adding the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 60 ℃, controlling the stirring speed to be 1200rpm, controlling the pH value of the solution in the reactor to be 10.1, keeping the temperature of 60 ℃ after dropwise adding the solution, reacting for 4 hours, and repeatedly cleaning and drying the generated product by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 550 ℃ for 3.5h in an air atmosphere, heating to 800 ℃ and sintering for 20h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 8
An oxide sodium ion battery anode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding 8% by mass of polystyrene into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia water (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the solution at 50 ℃ for reaction for 5 hours after dripping, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of the excessive components are mixed evenly,firstly sintering the mixture for 5 hours at 500 ℃ in an air atmosphere, then heating the mixture to 850 ℃ and sintering the mixture for 15 hours to obtain a target product, namely the oxide sodium-ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 9
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding polydopamine with the mass of 5.5% into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the solution at 50 ℃ for reaction for 5 hours after dripping, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of excessive sodium oxide, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, heating to 850 ℃ and sintering for 15h to obtain a target product, namely the oxide sodium ion battery anode material with a theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Example 10
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Adding soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving into water at a molar ratio of 1;
adding 6% by mass of poly (epoxypropyl methacrylate) into the aqueous solution by taking the theoretical mass of the formed hydroxide as 100%, and uniformly dispersing by ultrasonic to obtain a mixed solution; the concentration of soluble metal salt in the mixed solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the mixed solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the mixed solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the solution at 50 ℃ for reaction for 5 hours after dripping, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is a composite structure of nickel-manganese-iron hydroxide and polystyrene;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Dry mixing according to stoichiometric ratio, na 2 CO 3 3 percent of the sodium ion battery cathode material, sintering the mixture for 5 hours at 500 ℃ in an air atmosphere, heating the mixture to 850 ℃ and sintering the mixture for 15 hours to obtain a target product, namely the sodium ion battery cathode material with the theoretical chemical formula of Na [ Ni ] 0.33 Fe 0.33 Mn 0.33 ]O 2 。
Comparative example 1
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving the mixture into water according to the molar ratio of 1; the concentration of the soluble metal salt in the aqueous solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, the concentration of NaOH in the precipitation solution is 2mol/L,the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the aqueous solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the aqueous solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the temperature of 50 ℃ for reaction for 5 hours after the dripping of the solution is finished, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is nickel-manganese-iron hydroxide;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Mixing according to stoichiometric ratio, na 2 CO 3 3% of excessive amount, uniformly mixing, sintering at 500 ℃ for 5h in an air atmosphere, and then heating to 850 ℃ for sintering for 15h to obtain a target product, namely the oxide sodium-ion battery positive electrode material.
Comparative example 2
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing soluble metal salt NiSO 4 、MnSO 4 And FeSO 4 Dissolving the mixture into water according to the molar ratio of 1; the concentration of the soluble metal salt in the aqueous solution is 1mol/L;
(2) Mixing NaOH solution with ammonia (NH) 3 ·H 2 O) are mixed to prepare a precipitation solution, wherein the concentration of NaOH in the precipitation solution is 2mol/L, and the concentration of ammonia water is 0.24mol/L;
simultaneously dripping the aqueous solution and the precipitation solution into a continuous reactor, controlling the feeding speed of the aqueous solution and the precipitation solution to be 10mL/min, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 1000rpm, controlling the pH value of the solution in the reactor to be 10, keeping the temperature of 50 ℃ for reaction for 5 hours after the dripping of the solution is finished, and washing and drying the generated product for multiple times by deionized water to obtain a metal M precursor which is nickel-manganese-iron hydroxide;
(3) Mixing the metal M precursor obtained in the step (2) with Na 2 CO 3 Mixing according to stoichiometric ratio, na 2 CO 3 3 percent of the excessive oxide is mixed evenly, and then the mixture is sintered for 5 hours at 500 ℃ in the air atmosphere and is heated to 850 ℃ for sintering for 15 hours to obtain the layered oxide;
(4) And (4) uniformly mixing the layered oxide obtained in the step (3) with polystyrene with the mass of 4% by taking the mass of the layered oxide as 100%, then placing the mixture into a muffle furnace, and sintering the mixture for 3 hours at 800 ℃ in an air atmosphere to obtain the oxide sodium-ion battery cathode material.
Comparative example 3. Mu.l
An oxide sodium ion battery anode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Preparing the layered oxide by adopting a coprecipitation method, wherein the specific steps are the same as the steps (1) to (3) in the comparative example 2, so as to obtain the layered oxide;
(2) And (2) uniformly mixing the layered oxide with polystyrene with the mass of 4% by taking the mass of the layered oxide as 100%, then placing the mixture into a muffle furnace, and sintering the mixture for 3 hours at 800 ℃ in a nitrogen atmosphere to obtain the oxide sodium-ion battery cathode material.
Comparative example 4
An oxide sodium-ion battery positive electrode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Preparing the layered oxide by adopting a coprecipitation method, wherein the specific steps are the same as the steps (1) to (3) in the comparative example 2, so as to obtain the layered oxide;
(2) Dispersing 12g of the layered oxide obtained in the step (1) into 2L of ethanol/acetonitrile solution (the volume ratio of ethanol to acetonitrile is 3:1), adding 40mL of ammonia water (30%), and stirring for 30min to obtain solution A; adding 15mL of tetrabutyl titanate into another ethanol/acetonitrile solution (1L, the volume ratio of ethanol to acetonitrile is 3:1), and stirring for 10min to obtain a solution B; adding the solution B into the solution A, stirring for 30min, vacuum-filtering to separate the product, vacuum-drying the obtained anode material at 80 ℃, and sintering at 450 ℃ in air for 3h to obtain TiO 2 The coated layered oxide is the anode material of the sodium-ion battery.
The performance of the oxide sodium-ion battery positive electrode materials provided in examples 1 to 10 and comparative examples 1 to 4 was tested by the following specific method:
1. testing of crystal structure
An X-ray diffractometer (XRD, shimadzu, XRD 6100) is used to test the crystal structure of the positive electrode material of the sodium-ion battery, wherein, the XRD pattern of the positive electrode material of the sodium-ion battery provided in example 1 is shown in fig. 1, and it can be known from fig. 1 that the positive electrode material of the sodium-ion battery has good crystallinity, high purity and no impurity peak.
2. Elemental analysis
The oxide sodium ion battery anode material is subjected to elemental analysis by adopting an inductively coupled plasma emission spectrometer (ICP, agilent 5100), and the sample preparation method comprises the following steps: putting 1.0g of a sample to be detected in a 50mL PTFE beaker, adding 3mL of concentrated nitric acid and 9mL of hydrochloric acid, heating for 30min at 260 ℃ on a hot plate, filtering, transferring to a 100mL volumetric flask, and fixing the volume to be detected; the ICP test was performed on the aforementioned test solutions, and the test results of examples 1 to 8 and comparative examples 1 to 2 are shown in table 1, for example:
TABLE 1
3. Electrochemical Performance test
Assembling the sodium-ion button cell by adopting the anode material of the oxide sodium-ion battery to be tested: mixing an oxide sodium ion battery positive electrode material, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to a mass ratio of 8; assembling the prepared positive pole piece and a sodium metal pole piece into a sodium ion button cell, dissolving sodium perchlorate with the concentration of 1M in Propylene Carbonate (PC)/fluoroethylene carbonate (FEC) (mass ratio 97, shenzhen friend research), and obtaining electrolyte; after the electricity-buckling assembly is completed, carrying out capacity and cycle test on a blue battery test system according to the following steps: standing for 2h; constant current charging and discharging, wherein the charging and discharging voltage interval is 2.0-4.0V, the cycle multiplying power is 0.5C and 2.0C respectively, and the rated gram capacity is 120mAh/g.
The test results are shown in table 2:
TABLE 2
The performance test data in table 2 show that, compared with the oxide sodium ion battery positive electrode material (comparative example 1) prepared by the conventional coprecipitation method, the high polymer material is introduced into the preparation method provided by the invention, and through the design and mutual synergistic cooperation of the high polymer material and the coprecipitation method, the obtained oxide sodium ion battery positive electrode material has significantly improved structural integrity, cycle stability and electrochemical performance, and as a positive electrode active material, the specific capacities of the oxide sodium ion battery positive electrode material under 0.1C, 0.5C, 1.0C, 2.0C and 5.0C are 138.1-138.7mAh/g, 126.9-128.6mAh/g, 116.6-118.2mAh/g, 99.2-100.5mAh/g and 84.2-89.8mAh/g respectively, the capacity of the battery positive electrode material at 0.5C cycle 100 cycles is 83.1-87.6%, the capacity retention rate of the battery at 2.0C cycle 300 cycles is 63.5-66.8%, and particularly the capacity retention rate of the oxide sodium ion battery positive electrode material at high performance is proved to have obvious retention rate in the aspect of the cycle structural integrity and the aspect of the positive electrode structure stability and the cycle stability are obviously improved.
In the preparation method provided by the invention, the metal M precursor obtained by coprecipitation reaction comprises a composite structure of a high polymer material and a metal hydroxide, a specific amount of the high polymer material is subjected to carbonization and oxidation reaction in a sintering process, the oxygen distribution and the oxygen distribution condition on the surface of an oxide are effectively regulated and controlled to form an oxygen-poor stable phase, a coating layer which is the same as the components of the bulk material, tightly combined and stable in structure is generated in situ, and the obtained oxide sodium-ion battery positive electrode material has a structure gradually transited from inside to outside and shows excellent structural integrity, stability and electrochemical performance. In comparative examples 2 to 3, if the preparation method defined in the present invention is not used, the conventional co-polymerization is first performedThe layered oxide is prepared by a precipitation method, and then is mixed with the high molecular material and sintered again, the carbonization/oxidation reaction of the high molecular material in the comparative example 2 can not regulate and control the formation of the oxide and the surface oxygen distribution, and a specific oxygen-poor structure can not be formed, so that the electrochemical performance of the anode material is poor; the polymer material in the comparative example 3 forms a carbon coating layer in sintering, which can improve the conductivity of the material and the rate capability of the material, but cannot provide durable protection for the material (here, polystyrene is a microsphere, and may not form a uniform carbon coating layer); comparative example 4 TiO was formed on the surface of a layered oxide 2 The coating, this layer is different with the component of oxide body, and the interface problem that brings from this has influenced cathode material's circulation stability, leads to the coating material can't provide enough lasting protection to body material, consequently, body material's cyclicity can have certain improvement, nevertheless can't reach the protective effect of oxygen deficient layer protection to body material.
The applicant states that the present invention is illustrated by the above examples to the oxide sodium ion battery positive electrode material of the present invention, and the preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific forms, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the oxide sodium-ion battery anode material is characterized in that the chemical formula of the oxide sodium-ion battery anode material is NaxMO 2 Wherein x is more than 0 and less than or equal to 1,M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn;
the preparation method comprises the following steps:
(1) Mixing soluble metal M salt, a high polymer material and water to obtain a mixed solution;
(2) Reacting the mixed solution obtained in the step (1) with a precipitation solution to obtain a metal M precursor;
(3) And (3) mixing the metal M precursor obtained in the step (2) with a sodium source, and then sintering under an aerobic condition to obtain the oxide sodium-ion battery anode material.
2. The method according to claim 1, wherein the soluble metal M salt in step (1) comprises soluble nickel salt and soluble manganese salt, and at least one of soluble iron salt, soluble cobalt salt, soluble copper salt, soluble titanium salt and soluble tin salt;
preferably, the soluble metal M salt of step (1) comprises a combination of a soluble nickel salt, a soluble manganese salt and a soluble iron salt;
preferably, the soluble nickel salt comprises any one of nickel sulfate, nickel chloride and nickel nitrate or a combination of at least two of the nickel sulfate, the nickel chloride and the nickel nitrate;
preferably, the soluble manganese salt comprises any one of manganese sulfate, manganese chloride, manganese nitrate or a combination of at least two of the manganese sulfate, manganese chloride and manganese nitrate;
preferably, the soluble iron salt comprises any one of ferrous sulfate, ferrous chloride and ferrous nitrate or a combination of at least two of the two;
preferably, the concentration of the soluble metal M salt in the mixed solution in the step (1) is 0.5-2.5mol/L.
3. The preparation method according to claim 1 or 2, wherein the polymer material in step (1) comprises any one of polystyrene, polydopamine, polyacrylate or a combination of at least two of the same;
preferably, the mass of the polymer material is 0.2 to 6% based on 100% of the mass of the hydroxide prepared from the soluble metal M salt and the precipitation solution.
4. The method according to any one of claims 1 to 3, wherein a combination of a precipitant and a complexing agent is included in the precipitation solution of step (2);
preferably, the precipitating agent comprises sodium hydroxide and/or potassium hydroxide;
preferably, the complexing agent comprises any one or a combination of at least two of ammonia water, sodium citrate, disodium ethylene diamine tetraacetate and tetrasodium ethylene diamine tetraacetate;
preferably, the precipitation solution in step (2) comprises a combination of sodium hydroxide and ammonia water;
preferably, the concentration of the complexing agent in the precipitation solution is 0.12-2mol/L;
preferably, the amount of the precipitant in the precipitation solution is 2.0 to 2.2mol based on 1mol of the soluble metal M salt in the mixed solution.
5. The method according to any one of claims 1 to 4, wherein the temperature of the reaction in step (2) is 40 to 60 ℃;
preferably, the reaction time of the step (2) is 3-7h;
preferably, the reaction of step (2) has a pH of 8 to 11.5;
preferably, the reaction of step (2) is carried out under stirring conditions;
preferably, the stirring speed is 800-1200rpm;
preferably, the reaction in step (2) further comprises the steps of washing and drying after the reaction is completed.
6. The production method according to any one of claims 1 to 5, wherein the sodium source in the step (3) is selected from any one of sodium oxide, sodium hydroxide, sodium salt or a combination of at least two thereof;
preferably, the sodium source in step (3) comprises any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate and sodium chloride;
preferably, the mixing method in step (3) is grinding mixing;
preferably, the sintering in the step (3) comprises a first stage sintering and a second stage sintering which are sequentially carried out, wherein the temperature of the first stage sintering is lower than that of the second stage sintering;
preferably, the temperature of the first stage sintering is 400-550 ℃;
preferably, the time of the first sintering stage is 3-7h;
preferably, the temperature of the second section sintering is 750-900 ℃;
preferably, the time for the second stage sintering is 10-25h.
7. The method according to any one of claims 1 to 6, comprising in particular the steps of:
(1) Mixing soluble metal M salt, a high polymer material and water to obtain a mixed solution; the concentration of soluble metal M salt in the mixed solution is 0.5-2.5mol/L;
the high polymer material comprises any one of polystyrene, polydopamine and polyacrylate or the combination of at least two of the polystyrene, the polydopamine and the polyacrylate; the mass of the high polymer material is 0.2-6% based on 100% of the mass of the hydroxide prepared from the soluble metal M salt and the precipitation solution;
(2) Reacting the mixed solution obtained in the step (1) with a precipitation solution, wherein the pH value of the reaction is 8-11.5, the temperature is 40-60 ℃, the time is 3-7h, and the generated product is washed and dried to obtain a metal M precursor;
the precipitation solution comprises a combination of sodium hydroxide and ammonia water, and the concentration of the ammonia water in the precipitation solution is 0.12-2mol/L; based on 1mol of soluble metal M salt in the mixed solution, 2.0-2.2mol of sodium hydroxide is added;
(3) And (3) uniformly mixing the metal M precursor obtained in the step (2) with a sodium source, sintering for 3-7h at 400-550 ℃ under an aerobic condition, and then heating to 750-900 ℃ for sintering for 10-25h to obtain the oxide sodium-ion battery anode material.
8. An oxide sodium-ion battery positive electrode material, which is prepared by the preparation method according to any one of claims 1 to 7;
preferably, the chemical formula of the oxide sodium-ion battery positive electrode material is NaxMO 2 Wherein x is 0.5-1,M selected from the group consisting of Ni, co, cu, and Ti,Any one or combination of at least two of Mn, fe, cu, ti and Sn;
preferably, the chemical formula of the oxide sodium-ion battery positive electrode material is NaxNiyMnzM' (1-y-z) O 2 (ii) a Wherein, 0 < y < 1,0 < z < 1,M' is selected from any one or the combination of at least two of Co, fe, cu, ti and Sn;
preferably, the chemical formula of the oxide sodium-ion battery positive electrode material is NaxNiyMnzFe (1-y-z) O 2 。
9. Use of the oxide sodium-ion battery positive electrode material of claim 8 in an electrochemical device;
preferably, the electrochemical device comprises a sodium ion battery or a capacitor.
10. A sodium ion battery comprising the oxide sodium ion battery positive electrode material of claim 8.
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